本文關(guān)鍵詞： 單分子磁體 熒光 3d-4f 多功能材料 有效能壘　出處：《江西理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：稀土元素具有獨(dú)特的光、電、磁等理化性質(zhì),在多功能材料制備中具有重要的應(yīng)用價(jià)值。一直以來(lái)大多數(shù)研究者往往將稀土配合物作為單一的功能材料使用,很少有研究者同時(shí)利用稀土離子的磁性能和熒光性能制備磁性-發(fā)光雙功能分子材料。鑒于3d-4f異金屬配合物磁性-發(fā)光雙功能分子材料的研究還比較少,本論文選用l,1,1-三(2-氨基乙基)胺(tren)為骨架引入2-羥基-3-甲氧基苯甲醛、3-醛基水楊酸,并通過(guò)還原得到兩個(gè)胺酚多齒配體(amine-phenol ligands),通過(guò)配體分割合成法構(gòu)筑了9個(gè)3d-4f異金屬多核配合物。通過(guò)單晶衍射儀、元素分析、紅外光譜、熒光光譜、X-射線粉末衍射儀、TG以及磁性測(cè)量系統(tǒng)等多種表征手段,對(duì)3d-4f異金屬多核配合物的結(jié)構(gòu)、光譜性質(zhì)和磁性能進(jìn)行了詳細(xì)的研究。第一章,綜述了本文工作的研究背景及相關(guān)現(xiàn)狀,簡(jiǎn)要的總結(jié)和評(píng)述了3d-4f異金屬單分子磁體的研究進(jìn)展、磁性-發(fā)光雙功能分子材料的研究進(jìn)展。結(jié)合國(guó)內(nèi)外研究的相關(guān)現(xiàn)狀,系統(tǒng)的闡明了本論文的選題依據(jù)以及所取得的研究進(jìn)展。第二章,主要研究了以tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine1為配體通過(guò)雙溶劑(甲醇:三氯甲烷=1:1)恒溫?fù)]發(fā)法合成了6個(gè)3d-4f異金屬三核配合物[M2LnL2]·2ClO4·H2O(M=Ni,Ln=Gd(1),Tb(2),Dy(3);M=Zn,Ln=Gd(4),Tb(5),Dy(6)),并對(duì)其晶體結(jié)構(gòu)、光譜性質(zhì)、磁性等進(jìn)行了詳細(xì)的表征。單晶測(cè)試結(jié)果表明配合物1-6屬于同構(gòu)物,屬于單斜晶系、P21/c空間群。磁性研究表明,配合物1-3中NiII與LnIII金屬離子之間存在鐵磁耦合作用,配合物3表現(xiàn)出了非常弱的場(chǎng)誘導(dǎo)慢磁弛豫行為,且具有多個(gè)磁弛豫過(guò)程。配合物5和6表現(xiàn)出了典型的場(chǎng)誘導(dǎo)慢磁弛豫行為且在2 K溫度下的場(chǎng)依賴的磁化強(qiáng)度曲線中配合物6觀察到了蝴蝶型的磁滯回線。在50 kG和2.0 K時(shí)配合物1的磁熵變達(dá)到了9.31 J kg-1K-1。熒光光譜分析表明,有機(jī)配體L3-可以作為天線配體敏化稀土離子發(fā)光,配合物3、5、6三者都具有稀土離子特征的窄帶發(fā)射峰。第三章,主要通過(guò)配體分割合成法得到了3個(gè)基于胺酚多齒配體的3d-4f異金屬六核配合物[Ni4Ln2(L1)4(NO3)2]·4NO3(Ln=Gd(7),Tb(8),Dy(9)),并對(duì)其晶體結(jié)構(gòu)、熱穩(wěn)定性、磁性等進(jìn)行了詳細(xì)的表征。單晶測(cè)試結(jié)果表明配合物7屬于三斜晶系、P-1空間群,配合物8和9屬于三方晶系、R-3空間群。磁性研究表明,配合物7-9中NiII與LnIII金屬離子之間存在弱鐵磁耦合作用,配合物9表現(xiàn)出了非常弱的場(chǎng)誘導(dǎo)慢磁弛豫行為。
[Abstract]:Rare earth elements have unique physical and chemical properties, such as light, electricity, magnetic and so on, which have important application value in the preparation of multifunctional materials. Most researchers have always used rare earth complexes as a single functional material. Few researchers have made use of the magnetic properties and fluorescence properties of rare earth ions to prepare magneto-luminescent bifunctional molecular materials at the same time. . In this paper, we introduce 2-hydroxy-3-methoxybenzaldehyde 3-aldosalicylic acid as the skeleton. Two amine-phenol ligandswere obtained by reduction. Nine 3d-4f heterometallic polynuclear complexes were constructed by ligand fractionation synthesis method, which were characterized by single crystal diffractometer, elemental analysis, infrared spectrum, fluorescence spectrum and X-ray powder diffractometer. The structure, spectral properties and magnetic properties of 3d-4f heterometallic polynuclear complexes were investigated by TG and magnetic measurement system. Chapter 1. The research background and current situation of this paper are reviewed, and the research progress of 3d-4f isomeric monolayer magnets is briefly reviewed. The research progress of magnetic-luminescent bifunctional molecular materials. Combined with the current situation of domestic and foreign research, the basis of this thesis and the research progress made are systematically expounded. Chapter 2. The use of tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine1 as ligand was studied in this paper. Synthesis of six 3d-4f heterometallic trinuclear complexes by isothermal volatilization with methanol: trichloromethane 1: 1). [M _ 2LnL _ 2] 路2ClO _ 4 路H _ 2O _ 2; The crystal structure and spectral properties of MZZN LnGdC4, TbC5 and Dy6 are also discussed in this paper, and their crystal structure and spectral properties are also discussed in this paper, and the crystal structure and spectral properties are also discussed in this paper. The results of single crystal test show that the complex 1-6 belongs to isomorphism and belongs to the monoclinic system P21 / c space group. The magnetic study shows that the complex 1-6 belongs to the isomorphism group and belongs to the monoclinic system P21 / c space group. Ferromagnetic coupling exists between NiII and LnIII metal ions in complexes 1-3, and complex 3 exhibits very weak field-induced slow magnetic relaxation behavior. The complexes 5 and 6 exhibit typical field-induced slow magnetic relaxation behavior. In the field-dependent magnetization curve at K temperature, the hysteresis loop of butterfly type was observed in complex 6. The magnetic entropy of complex 1 reached 9.31 J at 50 KG and 2.0 K. Kg-1K-1. fluorescence spectrum analysis showed that. Organic ligands L3- can be used as antenna ligands to sensitize the luminescence of rare earth ions. Three 3-d-4f hexaduclear heterometallic complexes based on polydentate ligands of aminophenol were synthesized by ligand partitioning synthesis. [The crystal structure and thermal stability of Ni4Ln2(L1)4(NO3)2 were studied. The magnetic properties were characterized in detail. The results of single crystal test showed that the complex 7 belongs to the trichroic crystal system and the complexes 8 and 9 belong to the rhombohedral crystal system R-3 space group. The magnetic study shows that the complex 7 belongs to the trichroic crystal system. There is a weak ferromagnetic coupling between NiII and LnIII metal ions in complex 7-9, and complex 9 exhibits very weak field-induced slow magnetic relaxation behavior.
【學(xué)位授予單位】：江西理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O641.4

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本文編號(hào)：1489858